Beneficiation of ilmenite ores

ABSTRACT

An ilmenite ore may be beneficiated by oxidation to yield a pseudobrookite-containing material, reduction of the oxidation product to give a material having at least 4% of its iron content in the ferric state, and leaching of the reduced material. Leaching is facilitated by the previous two steps. The beneficiate is suitable for chlorination under fluidised-bed reaction conditions to yield titanium tetrachloride, and the reactivity of the beneficiate in chlorination may be enhanced by preliminary calcination to 600* - 700*C.

United States Patent Robinson et al.

BENEFICIATION 0F ILMENITE ORES Inventors: Michael Robinson; Frank Clamp;

David Aberdeen; David Barry Mobbs, all of Grimsby, England Laporte Industries Limited, London, England Filed: Apr. 4, 1972 Appl. No.: 241,057

Assignee:

Foreign Application Priority Data Apr. 5, 1971 United Kingdom 8809/71 Jan. 7, 1972 United Kingdom 911/72 flmqflflynnr? r- US. Cl. 423/86; 75/1; 423/82; 423/610 Int. Cl...... C22b l/00; COlg 23/04; C21b 1/00 Field of Search 75/1 T; 423/74, 82, 86, 423/610 References Cited I UNITED STATES PATENTS 8/1938 Dawson et a1. 75/1 5/1969 Michal et a1. 75/1 [451 July 29,1975

3,597,189 8/1971 Sinha et al.. 75/1 3,649,243 3/1972 Williams et a1. 75/1 3,660,029 5/1972 Naguib 75/1 FOREIGN PATENTS OR APPLICATIONS 215,866 7/1958 Australia 75/1 723,087 12/1965 Canada 75/1 Primary Examiner-Winston A. Douglas Assistant Examiner-Mark Bell Attorney, Agent, or F irm-Kane, Dalsimer, Kane, Sullivan and Kurucz [57] ABSTRACT 18 Claims, N0 Drawings BENEFICIATION OF ILMENITE ORES This invention relates to a process for the beneficiation of ilmenite ores, and is especially concerned with the production of a suitable feed material for the manufacture of titanium tetrachloride by chlorination under fluidised-bed reaction conditions.

In the production of titanium tetrachloride by flui dised-bed chlorination, the overall efficiency of the process is impaired when some of the particles present in the chlorinator are so small that they are entrained in the fluidising gas and are carried out of the reactor either unreacted or incompletely reacted. This can either arise from the presence in the starting material of particles which are too small, or from breakdown of the starting material under the fluidised-bed reaction conditions to yield fines. Inadequate particle size in the starting material can result from grinding the ore material before it is beneficiated, and is also observed when, following undesirable dissolution of titanium in a leaching operation, it proves necessary to effect some reprecipitation.

A number of previously proposed processes for beneficiating titaniferous ore materials involve oxidising the ore to convert its iron content entirely to the ferric state. reducing the oxidised material so as to convert its iron content, either wholly or in part, to metallic iron, and finally leaching the reduced product. In a recent proposal, it has been suggested that the reduction should not be carried beyond the stage in which metallic iron constitutes 20% by weight of the reduced product.

The present invention is based in part on the observation that the tendency for breakdown of the beneficiated product in a fluidised-bed to yield fines is associated with the presence of metallic iron in the reduced material prior to the leaching stage. It has been found that the product obtained by leaching material that contains metallic iron contains cavities having diameters of about l microns or more, and it is believed that the presence of these cavities is responsible for the undesirable breakdown characteristics of such beneficiates under fluidised-bed reaction conditions.

The present invention provides a process for beneficiating an ilmenite ore, which comprises oxidising the ilmenite to yield a material of which at least by weight has a crystal structure of the pseudobrookite type, reducing the said material to yield a material hav ing at least 4% of its iron content (calculated as Fe) in the ferric state, and leaching the reduced material so obtained to yield a beneficiated titaniferous material.

It has been found that, by ensuring that at least 4% of the iron content of the material remains in the ferric state, no detectable matallic iron is formed under typical reduction conditions.

As a result of the formation of material having a structure of the pseudobrookite crystallographic type (hereinafter termed merely pseudobrookite for convenience), the reduced material formed subsequently is very readily leachable, making it possible to obtain a beneficiated product having a high titanium dioxide content, with very little loss of titanium values in the leaching step. Typically, the process of the invention leads to a product having a titanium dioxide content of 9293%, with 95-98% efficiency of recovery of titanium values from the reduced material. In the case of certain ilmenites, for example, Western Australian ilmenites, even better results have been obtained.

The formation of pseudobrookite may be brought about by contacting the ilmenite with oxygen or, preferably, an oxygen-containing gas, at an elevated temperature. Conveniently, the pseudobrookite is formed by heating the ilmenite ore in air.

The rate of formation of pseudobrookite is very strongly temperature-dependent. At 875C., for example, the desired quantity of pseudobrookite is not formed, at least with the majority of ilmenites, in an acceptable reaction time. At 900C, on the other hand, the rate of formation of pseudobrookite is very much more rapid, and the desired quantity can be formed in an acceptable reaction time. Advantageously, therefore, the formation of pseudobrookite is carried out at a temperature of at least 900C, and preferably at least 925C. At 950C, which has been found to be an especially suitable oxidation temperature, oxidation for a period of 40 minutes to 1% hours results in a final beneficiated product having very desirable properties. At 1000C., oxidation for 30 to 60 minutes is sufficient to yield a product consisting substantially wholly of pseudobrookite and rutile. At lower temperatures and relatively short times the oxidised material will usually be found to contain some haematite in addition to the pseudobrookite and rutile.

The maximum temperature at which the formation of pseudobrookite may be effected is largely determined by the need to avoid excessive sintering of the ore material. From this point of view, it is preferable that the temperature of the ore material should not exceed lO00C.

In certain circumstances, it may be found that the rate of formation of pseudobrookite as a function of temperature is affected to a small extent by the presence of artificially added materials in admixture with the ilmenite ore, or by the presence in the ore of a typically large quantities of impurities The formation of pseudobrookite may be effected in the presence of a compound of lithium, sodium, magnesium, zirconium, or zinc, preferably in ihe presence of a lithium compound. Such compounds serve to promote the formation of pseudobrookite and enable that stage of the process of the invention to be carried out at relatively low temperatures. If desired, the promoters may instead. be used to reduce the time required for the formation of pseudobrookite at a given temperature, or for a combination of these purposes. The discovery of pseudobrookite promoters does not form part of the present invention, but has been described in order to illustrate the effects obtainable with the use of additives.

Whilst it is only necessary to form 20% by weight of pseudobrookite in order to bring about an improvement in the leachability of the reduced material obtained subsequently, the proportion of pseudobrookite formed is advantageously at least 30% (and preferably at least 50%), estimated by X-ray analysis. It will generally be found to be desirable to carry out the first stage of the process under such conditions that the theoretical maximum proportion of pseudobrookite is approached. Typically, when the pseudobrookite is formed by oxidation, the theoretical maximum proportion will be in the range of from about 60% to about by weight, although it may be as high as in some cases.

The pseudobrookite formed from ilmenite will have a composition in the range TiFe- O Ti- FeO depending on the composition of the original ilmenite and on the extent of oxidation occurring in the first stage of the process. If oxidation of the iron content of the original ilmenite is substantially complete. the pseudobrookite will have the composition TiFe O The crystal structure of that material is well-known and is described, for example, by Pauling in Z. Kristall, volume 73 (1930), pages 97 to 112. Other materials in the composition range given above have closely similar crystal structures (see Akimoto et al., Nature volume 179 (1957), pages 37 and 38).

The pseudobrookite content of a given sample may be measured by comparing the X-ray diffraction pattern of the sample with patterns obtained using standard samples containing known proportions of the same kind of pseudobrookite. Akimoto et al. describe a method of preparing different pseudobrookites within the composition range TiFe O Ti FeO by heating a mixture of ferric oxide, titanium dioxide, and metallic iron to 1 150C. and thereafter quenching the hot mixture. The total iron and titanium contents of the standard pseudobrookite-containing sample should be in the same ratio by weight as in the original ilmenite. This can be achieved by mixing the synthetic pseudobrookite with appropriate amounts of TiO and/or Fe It should be noted that, using the foregoing method, it will in general be found that there will be no appreciable detection unless the pseudobrookite content is about 5% by weight or above.

The formation of pseudobrookite may be carried out in any suitable apparatus, for example, in a rotary kiln, which may be operated either co-current or countercurrent.

The reduction reaction may be carried out at a temperature in the range of from 800 to 1000C., advantageously from 850 to 950C. in some cases, temperatures of from 900 to 950C. give optimum results. The use of temperatures in excess of 1000C. leads to increasing difficulties in preventing excessive reduction. Preferably, the material containing pseudobrookite is raised to the desired reduction temperature rapidly. The rate of attainment of the reduction temperature is dependent principally on the design of the reduction apparatus, but it is preferable to transfer the material containing pseudobrookite into the reduction zone while the material is still hot, so lessening the time taken for the material to reach the desired reduction temperature.

The reduction step should be carried out in an oxygen-deficient atmosphere, say, about 1% of oxygen by volume, and the reducing agent should be present in excess, taking into accound the oxygen derived from the reactants and any other oxygen that may be present in the reaction apparatus.

As is explained hereinbefore it is essential that the reduced material should contain no detectable metallic iron, and this leads in turn to the requirement that at least 4% of the iron content of the reduced material must remain in the ferric state. Although the proportion of trivalent iron in the reduced material can exceed 4%, a relatively lengthy leaching operation is required at high proportions of ferric iron. Also, pseudobrookite itself is not readily leachable, and the presence of pseudobrookite in the reduced material leads to a leached product having inferior titanium dioxide content. Accordingly, the reduction conditions are advantageously such that the reduction product contains substantially no detectable pseudobrookite (which implies that notmore than 5% by weight of pseudobrookite is present). The reductionproduct then consists predominantly of ilmenite and rutile. ln principle. it is desirable to eliminate all of the pseudobrookite, but broadly similar results are obtained with pseudobrookite contents of up to about 5% by weight.

in general, optimum titanium dioxide content in the leached material is obtained if the reduction reaction is not continued after the pseudobrookite has been eliminated. it is believed that the leaching characteristics of the reduced material are related to its porosity and crystallinity. It is also believed that the material possesses the optimum properties in terms of porosity and crystallinity when the pseudobrookite phase has just disappeared. It will frequently be the case, however, that the ferric iron content of the material is so high at that stage that the required leaching time will be inconveniently or impracticably long. The appreciation of the desirability of discontinuing the reduction reaction when the pseudobrookite has disappeared does not form part of the present invention.

The maximum proportion of the iron content remaining in the ferric state when elimination of pseudobrookite is substantially complete varies according to the type of ore in question, being about 18% in the case of Western Australian ilmenite, about 40% in the case of Norwegian ilmenite, and about l 1% in the case of Quilon ilmenite. It will usually be found advantageous, however, to decrease the proportion of ferric iron below these maximum figures. In the case of Western Australian ilmenite, the reduction is advantageously containued until a proportion of from 8 to 12% of the iron content of the material is in the ferric state. more generally, if the reduction stage is carried out under such conditionsthat not more than 10%, and'preferably at least 8%, and preferably at least 8%, of the iron content of the reduction product is in the ferric state, good results will be obtained. 3

The following discussion of the porosity and crystallinity of the reduction product, and of the temperature control needed to obtain and preserve good porosity and crystallinity, is based on appreciations which do not form part of the present invention. When the desired extent of the reduction has been achieved, the temperature of the reduced material should be quickly lowered, advantageously by discharging the hot reduced material into a cooling zone. If the temperature of the reduced material remains high after the reduction is complete, especially if its temperature is then relatively high, its leaching characteristics will suffer. This deterioration is believed to be associated with changes in porosity and crystallinity that take place if the material is maintained at a high temperature with no significant chemical reaction occurring. Similar changes (which involve increasing pore size and development of crystallinity) do in fact take place to some extent if the material is maintained hot for any length of time after elimination of the pseudobrookite, but their effect will generally becompensated by the concomitant removal of ferric iron, provided that reduction still continues while the material is hot.

The association betweenleachability and porosity has already been mentionedalt has been found that the porosity of the reduced product in the size range 0.04

to 2 microns is a useful guide to its leachability. The percentage porosity of a material is given by the expression:

(pore volume/apparent volume) X 100% The pore size distribution in a material may be measured by the well-known technique of mercury porosimetry.

Generally, the reduced product will be readily leachable if it has at least 7% porosity in the size range 0.04 to 2 microns. Desirably, the porosity in that range is at least 8%. In principle, materials having even higher porosities, say of the order of 10% or more, will be more readily leachable. As pointed out hereinbefore, however, difficulties can arise in endeavouring to combine high porosity with low ferric iron content.

If the temperature of the material is not quickly lowered when the reduction is complete, the pore size distribution will in general not satisfy the conditions laid down in the preceding paragraph.

If the material is to be discharged from the reduction apparatus when the pseudobrookite has been eliminated, then it is preferable to attain a relatively high temperature at that point. If, on the other hand, the reduction is to be continued after the elimination of pseudobrookite, it will generally be advisable to operate with a relatively lower maximum temperature, although it is again preferable that elimination of pseudobrookite should take place at or near the maximum temperature employed. If the material is to remain in the apparatus after elimination of pseudobrookite, it must be emphasised that the desirable crystallinity and porosity will be lost if the temperature remains high with no reduction occurring.

The reduction stage of the process may be effected using a gaseous reducing agent, for example, hydrogen or a hydrocarbon gas such as methane. A preferred gaseous reducing agent is carbon monoxide. Typically, when the reducing agent comprises carbon monoxide, the reduction may be effected at about 800C, as compared with about 900C. for methane reduction. Temperatures as low as 700C. may be employed when the reducing agent comprises hydrogen. Reduction with a gaseous agent may be effected under fluidised-bed reaction conditions.

The reduction may instead be effected by contacting the pseudobrookite-containing material with a solid carbonaceous reducing agent at an elevated temperature. Although the use of a gaseous reductant has the advantage that no solid/solid separation is needed after the reduction, the reaction will commonly proceed more rapidly when a gaseous agent for example, methane) is used, and especially careful control is then required in order to ensure that at least 4% by weight of the iron content of the reduced material is in the ferric state.

It will be appreciated that the reducing agent may be used in admixture with other substances which may assist in the reduction process. For example, hydrogen may be used in admixture with steam.

Any solid cabonaceous reducing agent may be used, but there should be present, preferably contained in the solid material, a quantity of material that is volatile under the conditions of the reaction. The presence of volatiles is essential if the reaction is to proceed at an adequate rate. If used alone, pure carbon containing no volatile matter, for example, calcined petroleum coke,

is extremely inefficient in bringing about the desired degree of reduction. The exact volatile content of the reducing agent is not critical, however, and substances having widely differing volatile contents produce similar effects in the reduction reaction, although the rate of reaction will not be the same in each case. [n general, the higher the volatile content of the reducing agent, the more rapid is the rate of reduction at a given temperature.

Examples of solid carbonaceous reducing agents which may be used include green coke, semi-coke, lignite, and the coal/coke mixture known as reject char. which is a material obtained in the low-temperature carbonisation of coal.

Advantageously, the reducing agent is coal, for example, anthracite. Any coal may be used, provided that it is non-caking under the conditions of the reaction. The diameter of certain coals to form cakes may be overcome by oxidising the coal for a period of from about /1 hour to about 1 /2 hours at a temperature in the range of from 200 400C, and such pre-oxidixed coal may be used in the process of the present invention.

With regard to the particle size of a solid carbonaceous reducing agent used in the reduction step, the limits are not critical. The most important factor governing the maximum particle size is the desirability of the surface area of the particles being sufficiently high to give reasonably reaction efficiency. If the reaction mixture is to be exposed to a gas stream, the use of very small particles (which might of course be entrained in the stream) should be avoided. Material having a suitable particle size can readily be obtained by grinding.

When an excess of a solid reducing agent is used, the reduced material may be separated by magnetic techniques from the unconsumed reducing agent.

Reduction with a solid reductant may be effected in any suitable apparatus. For example, a rotary kiln may be employed, and may be operated either co-current or counter-current.

Advantageously, the conditions in the reduction zone of the apparatus are such that the residence time of the material at the reduction temperature does not exceed 2 hours, and preferably does not exceed 1 /2 hours. Especially good results are obtained if the residence time at the desired temperature is from 1% to 1% hours.

The following Table sets out the limits within which the temperature profile may lie in a gas-fired filn using coal as reductant. The Table has been included for illustrative purposes only, and the limits set out therein from no part of the present invention.

Time (mins.) 0 25 35 50 Temp.

(C 500x 700fi0 800:60 900170 Time 60 7O 1 10 Temp. 9 l ()fiO 900fi0 850140 800:30 750fl0 In a process operated in accordance with the above Table, the reduction reaction will continue after elimination of pseudobrookite.

As a further example of a suitable temperature profile, it will sometimes be found advantageous to conduct the reduction in two stages, a first stage at a temperature of up to about 850C. followed by a second 7 stage at 900 950C. there being a fairly sharp rise in the temperature profile between the two stages. Again, such a temperature profile forms no part of the present invention.

It will be appreciated that there is a risk that a certain amount of re-oxidation will take place as a result of atmospheric air coming into contact with the reduced material while it is cooling. and it will generally be found advisable to take precautions to prevent any significant re-oxidation taking place, as such re-oxidation impairs the leaching characteristics of the material to some extent. For example, when a solid carbonaceous reducing agent is used, the reduction product is most preferably cooled out of contact with the atmosphere before being separated from any unconsumed reducing agent.

The material obtained by the process steps described hereinbefore is readily leachable and a wide variety of leaching techniques may therefore be employed. Typically, a single-stage treatment with a 25% excess (over the stoichiometric quantity required in respect of the iron values only), of l7 /z20% w/w hydrochloric acid for 3 to 4 hours at a temperature of from 100 to 108C. leads to a product having a titanium dioxide content of at least 90% with at least 95% recovery of titanium values, and with substantially no degradation of particle size. Although other mineral acids may be used, hydrochloric acid is the preferred leaching agent, and may be recovered from the residual leach liquor by a thermal decomposition process, for example, by the process disclosed in British Patent Specification No. 793,700.

It will generally be found that the reduced material is sufficiently reactive in leaching that a single-stage leaching treatment at normal atmospheric pressure is all that is required. Accordingly, it will usually be unnecessary to resort to more severe leaching conditions and systems, for example, multi-stage leaching, contin uous co-current, counter-current, or cross-current leaching systems, or the use of superatmospheric pressure. The reduced material will frequently be found to be sufficiently reactive that hydrochloric acid having a strength as low as will be adequate. Preferably, the strength of the hydrochloric acid does not exceed w/w.

It will generally be found that a single-stage acid leaching treatment (involving no replenishment of used acid) will not only remove almost all of the iron values, but will also remove significant quantities of impurity elements such as, for example, manganese, chromium, and vanadium. In any leaching operation in which the acid is not continually replenished, the strength of the leaching acid will decrease steadily as the leaching operation progresses. in this connection, it has been found that the rate of leaching at any given instant is a function not only of the prevailing acid strength at that instant, but also of the initial acid strength.

An example of an efficient leaching solution is an acidic solution that contains some ferrous iron initially, for example a solution of ferrous chloride in hydrochloric acid. in general, such a solution will produce similar results in terms of titanium dioxide yield and content to those obtained by using the same quantity of acid alone, but will produce such results in a shorter time.

A solution containing ferrous iron may be obtained in a variety of ways. For example, if a quantity of leached material is washed with hydrochloric acid solution, the wash liquor will contain some ferrous iron in solution, and that wash liquor may then be used as leachant. Instead, the acid leaching solution may contain residual leach liquor. In such a process, the residual leach liquor will eventually contain such a high concentration of ferrous iron as to be unsuitable for recycle. If a hydrochloric acid leaching solution is employed, the acid may be recovered from the residual leach liquor by a thermal decomposition process. for example, by the process described in British Patent Specification No. 793,700, and such a recovery process will be especially valuable when the residual leach liquor is unsuitable for direct recycle. The appreciation that an acidic solution ferrous ferroous iron is an efficient leachant forms no part of the present invention.

When a solid reducing agent is used, it is preferable to separate the reduction product from any unconsumed reducing agent before the leaching treatment is carried out. Advantageously the desired separation is effected by means of a magnetic separation technique. Such a separation process will also reduce the quantity of any gangue material that may be present, for example, silica sand.

The beneficiated titaniferous material resulting from the leaching step does not break down to yield fine particles under fluidised-bed chlorination conditions, at least to any substantial extent, and the chlorination reaction can therefore produce a high yield. Accordingly, the present invention also provides a process for the production of titanium tetrachloride which comprises forming from an ilmenite ore a material of which at least 20% by weight has a crystal structure of the pseudobrookite type, reducing the said material under such conditions that not less than 4% of the iron content of the reduced material (calculated as Fe) is in the ferric state, leaching the reduced material so obtained to yield a beneficiated titaniferous material, and chlorinating the beneficiated material under fluidised-bed reaction conditions.

The beneficiated material contains a very small proportion of material that is relatively resistant to leaching. Such material does tend to yield fines on breakdown, but has a crushing strength which is sufficiently high that the particles do not in practice break down to any substantial extent under the chlorination conditions.

Desirably, the material to be chlorinated has a mean particle diameter of at least 100 microns, with substantially none of the particles having a diameter of less than microns. It is a feature of the beneficiation process according to the present invention that the mean particle diameter of the beneficiated material is not substantially different from that of the ilmenite ore starting material. Accordingly, the particle size distribution of the ilmenite is advantageously such that the mean weight diameter is at least l00 microns, and that there are substantially no particles having a diameter of less than 65 microns.

After being leached, the material may be calcined to a temperature of from 600 to 700C. Before being calcined, the leached material will be washed to remove residual leach liquor.

Such calcination of the leached material enhances its reactivity (measured as described hereinafter) in subsequent chlorination under fluidised-bed reactioin conditions. I

The reactivity of the calcined material under fluidised-bed chlorination conditions is measured for the .2 hours prleferrabfily f? bout T78 lio lrf tained in chlorinating' natural"'rutile is of the oi'der'of 0.20 -0.24. Theyalue of the ratio for the product of the present invention'may' be as low as 0.25,or cveri' lower in some cases, indicating that the reactivity of the m'at erial is approaching that of natural rutile, andmay be of closely similar reactivity in some cases. The carbon monoxide and carbon dioxide contents' of the exhaust gases from the chlorinator may be determined by gasliquid chromatography. f I

The calcination may beeffec'ted in any suitable apparatus, and may be continued fora period offrorn v to Chlorination of the product may be effected, for example, in a fluidised-bed chlorinator having a diameter of cm. constructedof silica. The chlorine flow rate is such a reactor may be about l/min. :andthe'reaction temperature may be maintained'at 925:C.

with a bed having a depth of 135 B way of'jexam ple, a leached beneficiate was calcined atf600"C. and

then chlorinated under the conditionsdescribedin this paragraph. The CQ/ (CO+CQ ratio in the exhaust gases was found to be 0.25. By comparison, when a sample of the same leached beneficiate was chlorinated under the same conditions, butwithout being calcined at 600 700C. prior to chlorination, the value for the ratio was 0.34. Ara'tio of 0.34 was also obtained wheii,

. in another comparison experiment, the benefici'atewas calcined at a temperature in ex cess of 800C. before being chlorinated. v In the chlorination of material obtained in accor-. dance with the presentinvention, the chlorine utilisation is generally of the order of 100%. i V

Calcination in, accordance withthe present i v'ention is effective. in,thoroughly removing water from the leached beneficiate.

The invention also provides a reactive titaniferous material obtained by the process of the inventionand suitable for use, as afeed material in the productionof titanium tetrachloride byfluidised-bed chlorination.

The invention further provides a b en'eficiated titaniferous material obtair ied by a beneficiation process according to the invention. I

The bnefic iated materia-l has a porous structure, substantially all of the 'pores being below 2 microns in diameter. Thestructure is-generally free from large cavities and it is believedthat this contributes to the desirable behaviour of the material under fluidised-bed reaction conditions.-

The following Examples illustrate'the invention:

. EXAMPLEI i 2 Kg. of a sample of Western Australian ilmenite was brought up to 'lOO0C. and was roasted-in an oxidising atmosphere in a= gas"-fired furnace atthat :temperature for a period of one hour. The ilmenite was contained in shallow trays and the contents of the tra;ys were raked at frequent intervals throughout the oxidising treatment. Initially, the ilmenite ore was found by wet analysis td'contain 54.6% titanium calculated as TiO 17.0% ferric iron calculated as F6 0,, and 23.7% ferrcius iron calculated as FeO, each percentage being by weight. The "particle size distrubution of the ilmenite ore w as that'i9 9-.8% by weight of the material had particle s iie in therange of from 75 to 200 microns, the meanwei'ght'diameter being 160 microns. After'the oxidising roast, no Fe O could be detected on wet analysis, and X rayf examination showed the structure of the Q Q material t sqdby weight pseudo- .brookite with m I i ":thezreducingagent for oneportion, and 50 g. of pretile.

oxidised (2OOC-,,- /2 hour) medium-volatile caking coal as the reducing agent for the other portion.

On completion of the reduction stages, the crucibles were allowed to cool with the contents out of contact with air, and the contents were then separated magnetically into'ore and coal char fractions. Wet analysis of -the three ore fractions showed that they each contained in excess of 35.0% by weight ferrous iron calculated as FeO and about 4.0% by weight ferric iron calculated as Fe O that is to say, about 9% of the iron content was in the ferric state. None of the :ore fractions contained any detectable metallic iron; X-ray analysis showed that each ore fraction contained only ilmenite and ru- Eac hof ore fractions was then leached'in boiling l8%.w/wh'ydrochloric acid for 4 hours, the quantity of acid used in each case being 25% in excess of the stoiterial, and theefficiency of recovery of titanium, were determined in each case. The'results obtained are set out in the following table.

TiO- content Efficiency of Reducing Agent of beneficiate Ti0 recovery anthracite 91.7% 98% high-volatile coal 92.5% 96% medium-volatile coal 92.7% 35% The particle size of the final product was substan-' tially the same as that of the initial ilmenite sample, and the grains showed a porousstructure, generally free from large cavities.

EXAMPLE 2 Western Australian ilmenite was fed to a gas-fired rotary kiln, 0.55m; in diameter and 7.3m. in'length, at a rate of 45 kg. per hour, and was oxidisedin the kiln at 900C. by means of atmospheric air/The residence time of the ilmenite in the kiln was about 2 hours, and X-ray examination of the oxidiseed material showed it to comprise 35% by weight pseudobrookite together with rutile and haematite.

The oxidised material was mixed with 30% by weight of kibbled anthracite and heated in the kiln to 950C. over a period of one hour. During this period, the oxygen content of the exit gases from the kiln varied between 0.5 and l% by volume. The material was then discharged from the kiln and cooled out of contact with the atmosphere. After cooling, the reduced material was separated magnetically from the unconsumed anthracite. On wet analysis, the ore material was found to contain 38% by weight ferrous iron calculated as FeO and about 2'/z% by weight ferric iron calculated as Fe O with no detectable metallic iron, that is to say. 5.6% of the iron content of the material was in the ferric state.

The reduced material was then leached under the same conditions as described in Example 1, and the resulting beneficiated material was found to contain 92.6% by weight of TiO The efficiency of recovery of titanium in the leaching step was 98%.

No large cavities could be detected within the grains of the beneficiated material, which had a porous structure.

EXAMPLE 3 The process described in Example 1 was repeated using a quantity of Quilon ilmenite containing 60.3% by weight of titanium (calculated as TiO and using a quantity of Norwegian ilmenite having a titanium content of 44.6% (calculated as TiO Before being oxidised, the Norwegian ilmenite was sieved in order to remove particles smaller than 170 mesh (British Standard).

In each case, X-ray analysis of the oxidation product showed that it consisted predominantly of pseudobrookite with some rutile, and X-ray analysis of the reduction product showed the presence of ilmenite and a small proportion of rutile, with no pseudobrookite.

The reducing agent used in each case was non-Caking high-volatile bituminous coal, and wet analysis of the reduced ore material showed that its ferric iron content was 7.5% is the case of the Quilon ilmenite, and 7.6% in the case of the Norweigan ilmenite (each percentage being by weight and based on the total iron content of the material). Neither of the reduction products contained any detectable metallic iron.

The titanium dioxide contents of the final beneficiates, and efficiencies of recovery of titanium dioxide in the leaching step, were as follows: A

llmenite TiO content TiO, recovery Quilon 92.5% 95% Norwegian 92% 94% say, material having a structure of the pseudobrookite crystallographic type.

We claim:

1. A process for beneficiating an ilmenite ore, which comprises heating the ilmenite under oxidising conditions to yielda material of which at least 20% by weight comprises pseudobrookite, reducing the oxidised material to' yield a material having at least 4% of its iron content (calculated as Fe) in the ferric state, and leaching the said reduced material to yield a beneficiated titaniferous material.

2. A process according to claim 1, wherein the oxidation is effected at a temperature in the range of from 900 to l000C.

3. A process according to claim 1, wherein at,least 30% by weight of the oxidised material comprises pseudobrookite. I

4. A process according to claim 3, wherein at least 50% by weight of the oxidised material comprises pseudobrookite.

5. A process according to claim 4, wherein at least by weight of the oxidised material comprises pseudobrookite.

6. A process according to claim 1, wherein the pseudobrookite content of the oxidised material formed from the ilmenite is substantially equal to the theoretical maximum for the ilmenite.

7. A process according to claim 1, wherein the reduction is effected at a temperature of from 800 to l000C.

8. A process according to claim 1, wherein the reduced material contains substantially no detectable pseudobrookite.

9. A process according to claim 1, wherein the pseudobrookite content of the reduced material does not exceed 5% by weight.

10. A process according to claim 1, wherein from 4 to 10% of the iron content of the reduced material is in the ferric state. l

11. A process according to claim 10, wherein at least 8% of the iron content of the reduced material is 'in the nation is continued for a period of from A to 2 hours.

16. A process according to claim 1 wherein, prior to being leached, the reduced material is cooled in a nono'xidising environment.

17. A process according to claim 1, wherein the oxidation is effected by heating the ilmenite within the temperature range of from 900C. to l,000C. in the presence of an oxidizing agent selected from the group consisting of oxygen and oxygen-containing gasses.

18. A beneficiated titaniferous material whenever prepared by a process according to claim 1.

PATENT NO.

DATED INVENTOR(S) 1 At Col. 1,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION July 29, 1975 Michael Robinson et al.

It is certified that error appears in the above-identified patent'and that said Letters Patent are hereby corrected as shown below:

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change the word "matallic" to read metallic change the word "accound" to read account change the word "cabonaceous" to read carbonaceous change the word "diameter" to read tendency change the word "filn" to read kiln insert after the word "solution" containing after the word "ferrous" delete the word ferroous change the word "reactioin" to read reaction i change "178" to read 1/2 UNITED STATES PATENT OFFICE Page 2 CERTIFICATE OF CORRECTION PATENT NO. 1 3,897,537

DATED July 29, 1975 |NVENT 1 Michael Robinson et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

At Col. 10, line 4, change the word "distrubution" to read distribution At Col. 11, line 43, after "7.5%" change the word "is" to read in Signed and Sealed this seventh Day of 0ct0 ber1975 [SEAL] AHESI.

RUTH C. MASON C. MARSHALL DANN' Attesring Officer (ommissiuner oj'Patents and Trademarks 

1. A PROCESS FOR BENIFICATING AN ILMENTITE ORE, WHICH COMPRISES HEATING THE ILMENITE UNDER OXIDISING CONDITIONS TO YIELD A MATERIAL OF WHICH AT LEAST 20% BY WEIGHT COMPRISES PRESUDOBROOKITE, REDUCING THE OXIDISED MATERIAL TO YIELD A MATERIAL HAVING AT LEAST 4% OF ITS IRON CONTENCT (ALCULATED AS FE) IN THE FERRIC STATE, AND LEACHING THE SAID REDUCED MATERIAL TO YIELD A BENEFICIATED TITANIFEROUS MATERIAL.
 2. A process according to claim 1, wherein the oxidation is effected at a temperature in the range of from 900* to 1000*C.
 3. A process according to claim 1, wherein at least 30% by weight of the oxidised material comprises pseudobrookite.
 4. A process according to claim 3, wherein at least 50% by weight of the oxidised material comprises pseudobrookite.
 5. A process according to claim 4, wherein at least 60% by weight of the oxidised material comprises pseudobrookite.
 6. A process according to claim 1, wherein the pseudobrookite content of the oxidised material formed from the ilmenite is substantially equal to the theoretical maximum for the ilmenite.
 7. A process according to claim 1, wherein the reduction is effected at a temperature of from 800* to 1000*C.
 8. A process according to claim 1, wherein the reduced material contains substantially no detectable pseudobrookite.
 9. A process according to claim 1, wherein the pseudobrookite content of the reduced material does not exceed 5% by weight.
 10. A process according to claim 1, wherein from 4 to 10% of the iron content of the reduced material is in the ferric state.
 11. A process according to claim 10, wherein at least 8% of the iron content of the reduced material is in the ferric state.
 12. A process according to claim 1, wherein the ilmenite is a Western Australian ilmenite and from 8 to 12% of the iron content of the reduced material is in the ferric state.
 13. A process according to claim 1, wherein the reduced material is acid leached in a single-stage treatment without replenishment of used acid.
 14. A process according to claim 1, wherein said beneficiated material is calcined to a temperature of from 600* to 700*C.
 15. A process according to claim 14, wherein calcination is continued for a period of from 1/4 to 2 hours.
 16. A process according to claim 1 wherein, prior to being leached, the reduced material is cooled in a non-oxidising environment.
 17. A process according to claim 1, wherein the oxidation is effected by heating the ilmenite within the temperature range of from 900*C. to 1,000*C. in the presence of an oxidizing agent selected from the group consisting of oxygen and oxygen-containing gasses.
 18. A beneficiated titaniferous material whenever prepared by a process according to claim
 1. 